4′-Methyl-1H-14′,19′-dioxa-4′-aza­spiro­[indole-3,5′-tetra­cyclo­[18.4.0.02,6.08,13]tetra­cosa­ne]-1′(24′),8′,10′,12′,20′,22′-hexa­ene-2,7′(3H)-dione

Narayanan, S.; Srinivasan, T.; Purushothaman, S.; Raghunathan, R.; Velmurugan, D.

doi:10.1107/S1600536812046132

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3344

doi:10.1107/S1600536812046132

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4′-Methyl-1H-14′,19′-dioxa-4′-azaspiro[indole-3,5′-tetracyclo[18.4.0.0^2,6.0^8,13]tetracosane]-1′(24′),8′,10′,12′,20′,22′-hexaene-2,7′(3H)-dione

Sibi Narayanan,^a Thothadri Srinivasan,^a Santhanagopalan Purushothaman,^b Raghavachary Raghunathan ^b and Devadasan Velmurugan ^a ^*

^aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: shirai2011@gmail.com

(Received 23 October 2012; accepted 8 November 2012; online 14 November 2012)

In the title compound, C₂₉H₂₈N₂O₄, the indoline ring system is essentially planar, with a maximum deviation of 0.027 (2) Å; the carbonyl O atom lies 0.102 (1) Å out of the least-squares plane of the indole ring. The pyrrolidine ring adopts a C-envelope conformation, with a C atom displaced by 0.643 (2) Å from the mean plane formed by the remaining ring atoms. The pyrrolidine ring makes a dihedral angle of 86.1 (8)° with the indoline ring system. In the crystal, N—H⋯O hydrogen bonds result in the formation of cyclic centrosymmetric dimers [R₂²(8)]. C—H⋯π interactions also occur, leading to a chain along the b-axis direction. There is a rather weak π–π electron interaction between the pyrrazole and benzene rings, with a centroid–centroid distance of 3.765 (1) Å.

Related literature

For background to natural and synthetic pharmacologically active pyrrolidines, see: Waldmann (1995 ). For related structures, see: Ganesh et al. (2012 ); Narayanan et al. (2012 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₉H₂₈N₂O₄
M_r = 468.53
Triclinic, $[P \overline 1]$
a = 9.4223 (3) Å
b = 10.5115 (3) Å
c = 14.1754 (5) Å
α = 70.235 (2)°
β = 87.309 (3)°
γ = 69.065 (2)°
V = 1229.67 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.19 mm

Data collection

Bruker APEXII CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ) T_min = 0.979, T_max = 0.984
22180 measured reflections
5998 independent reflections
4260 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.147
S = 1.01
5998 reflections
317 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C14–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.86	1.96	2.8105 (17)	170
C26—H26⋯Cg4ⁱⁱ	0.93	2.91	3.617 (3)	134
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x, -y+2, -z.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812046132/pv2600sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046132/pv2600Isup2.hkl

checkCIF report

Comment top

Highly functionalized pyrrolidines have gained much interest in the past few years as they constitute main structural unit of many natural and synthetic pharmacologically active compounds (Waldmann, 1995). In continuation of our work on the crystal structure analysis of spiro-pyrrolidine derivatives (Narayanan et al., 2012), the crystal structure of the title compound has been carried out and the results are presented here.

The bond lengths and angles in the title molecule (Fig. 1) are within normal ranges and comparable to those found in a related structure (Ganesh et al., 2012). The indoline ring system (C4–C11/N2) is essentially planar, with maximum deviation of 0.027 (2) Å for atom C5; O2 lies 0.102 (1) Å out of the leastsquares plane of the indole ring. The pyrrolidine ring (C1–C4/N1) adopts a C1-envelop conformation with C1 0.643 (2) Å displaced from the mean-plane formed by the remaining ring atoms. The pyrrolidine ring makes a dihedral angle of 86.1 (8)° with the indoline ring system. The dihedral angle between the mean-planes of the pyrrolidine ring and the benzene ring (C24—C29) is 64.1 (1)°.

The crystal packing is stabilized by N—H···O, C—H···π and π–π interactions. N2—H2A···O2 hydrogen bonding results in a cyclic centrosymmetric dimer in R₂²(8) ring motif (Bernstein et al., 1995). There is a rather weak π–π electron interaction between the centroids of the pyrrazole (N2/C4/C5/C6/C11) and benzene (C14—C19) rings (Cg2···Cg4, respectively) with the centroid-centroid distance 3.765 (1) Å.

Related literature top

For background to natural and synthetic pharmacologically active pyrrolidines, see: Waldmann (1995). For related structures, see: Ganesh et al. (2012); Narayanan et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

A mixture of isatin (150 mg, 1 mmol), sarcosine (90 mg, 1 mmol) and (4E)-12,17-dioxatricyclo[16.4.0.0^6,11]docosa-1(22),4,6,8,10,18, 20-heptaen-3-one (300 mg 1.0 mmol) in toluene (20 ml) was refluxed under Dean-Stark reaction condition until the disappearance of starting materials as evidenced by TLC. The reaction mixture was concentrated in vacuo and extracted with water (50 ml) and dichloromethane (2x50 ml). The organic layer was washed with brine solution, dried with anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by column chromatography with hexane-ethylacetate (9:1) mixture to yield macrocycle in good yields. The product was dissolved in ethylacetate and heated for two minutes. The resulting solution was subjected to crystallization by slow evaporation of the solvent resulting in single crystals suitable for XRD studies.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. The crystal structure showing the formation of the centrosymmetric R₂²(8) dimer;; H atoms not involved in hydrogen bonding have been omitted for clarity. The dashed lines indicate hydrogen bonds. The atoms marked with an asterisk (*) are at the symmetry position (-x, 2 - y, 1 - z).

4'-Methyl-1H-14',19'-dioxa-4'-azaspiro[indole-3,5'- tetracyclo[18.4.0.0^2,6.0^8,13]tetracosane]-1'(24'),8',10',12',20',22'- hexaene-2,7'(3H)-dione top

Crystal data top

C₂₉H₂₈N₂O₄	Z = 2
M_r = 468.53	F(000) = 496
Triclinic, P1	D_x = 1.265 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4223 (3) Å	Cell parameters from 5998 reflections
b = 10.5115 (3) Å	θ = 1.5–28.3°
c = 14.1754 (5) Å	µ = 0.09 mm⁻¹
α = 70.235 (2)°	T = 293 K
β = 87.309 (3)°	Block, colorless
γ = 69.065 (2)°	0.25 × 0.22 × 0.19 mm
V = 1229.67 (7) Å³

Data collection top

Bruker APEXII CCD area detector diffractometer	5998 independent reflections
Radiation source: fine-focus sealed tube	4260 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and ϕ scans	θ_max = 28.3°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −12→12
T_min = 0.979, T_max = 0.984	k = −13→12
22180 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0689P)² + 0.3628P] where P = (F_o² + 2F_c²)/3
5998 reflections	(Δ/σ)_max < 0.001
317 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₉H₂₈N₂O₄	γ = 69.065 (2)°
M_r = 468.53	V = 1229.67 (7) Å³
Triclinic, P1	Z = 2
a = 9.4223 (3) Å	Mo Kα radiation
b = 10.5115 (3) Å	µ = 0.09 mm⁻¹
c = 14.1754 (5) Å	T = 293 K
α = 70.235 (2)°	0.25 × 0.22 × 0.19 mm
β = 87.309 (3)°

Data collection top

Bruker APEXII CCD area detector diffractometer	5998 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	4260 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.984	R_int = 0.027
22180 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.01	Δρ_max = 0.47 e Å⁻³
5998 reflections	Δρ_min = −0.27 e Å⁻³
317 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.44418 (17)	0.81009 (18)	0.29447 (12)	0.0442 (4)
H1A	0.3946	0.7414	0.3256	0.053*
H1B	0.5502	0.7575	0.2883	0.053*
C2	0.36234 (16)	0.91660 (17)	0.19251 (11)	0.0390 (3)
H2	0.4231	0.9763	0.1617	0.047*
C3	0.21938 (15)	1.01176 (16)	0.22618 (10)	0.0348 (3)
H3	0.1490	0.9592	0.2438	0.042*
C4	0.27685 (16)	1.01883 (17)	0.32641 (11)	0.0363 (3)
C5	0.16358 (16)	0.99095 (17)	0.40634 (11)	0.0388 (3)
C6	0.16331 (17)	1.21653 (18)	0.38333 (11)	0.0413 (3)
C7	0.1279 (2)	1.3514 (2)	0.39076 (15)	0.0548 (4)
H7	0.0538	1.3844	0.4314	0.066*
C8	0.2075 (2)	1.4365 (2)	0.33506 (16)	0.0624 (5)
H8	0.1861	1.5284	0.3383	0.075*
C9	0.3177 (2)	1.3870 (2)	0.27514 (16)	0.0591 (5)
H9	0.3700	1.4456	0.2389	0.071*
C10	0.35165 (19)	1.25080 (19)	0.26815 (13)	0.0483 (4)
H10	0.4261	1.2177	0.2277	0.058*
C11	0.27254 (16)	1.16546 (17)	0.32249 (11)	0.0391 (3)
C12	0.4820 (2)	0.8338 (2)	0.45746 (14)	0.0600 (5)
H12A	0.4254	0.7730	0.4891	0.090*
H12B	0.4661	0.9054	0.4886	0.090*
H12C	0.5886	0.7756	0.4648	0.090*
C13	0.13484 (17)	1.15881 (17)	0.14799 (11)	0.0410 (3)
C14	−0.01066 (18)	1.25884 (17)	0.17087 (12)	0.0431 (4)
C15	−0.0379 (2)	1.4067 (2)	0.13226 (14)	0.0559 (5)
H15	0.0331	1.4388	0.0936	0.067*
C16	−0.1679 (3)	1.5065 (2)	0.15010 (19)	0.0705 (6)
H16	−0.1857	1.6052	0.1224	0.085*
C17	−0.2714 (3)	1.4584 (2)	0.20962 (18)	0.0714 (6)
H17	−0.3574	1.5253	0.2238	0.086*
C18	−0.2492 (2)	1.3136 (2)	0.24813 (15)	0.0605 (5)
H18	−0.3201	1.2826	0.2878	0.073*
C19	−0.12012 (18)	1.21319 (18)	0.22752 (13)	0.0465 (4)
C20	−0.2101 (2)	1.0135 (2)	0.29678 (16)	0.0590 (5)
H20A	−0.3031	1.0661	0.2523	0.071*
H20B	−0.2321	1.0224	0.3623	0.071*
C21	−0.1499 (2)	0.8579 (2)	0.30534 (19)	0.0699 (6)
H21A	−0.0474	0.8133	0.3382	0.084*
H21B	−0.2122	0.8103	0.3488	0.084*
C22	−0.1449 (3)	0.8287 (4)	0.2094 (2)	0.0923 (8)
H22A	−0.1226	0.7257	0.2263	0.111*
H22B	−0.2466	0.8790	0.1751	0.111*
C23	−0.0380 (3)	0.8677 (3)	0.13700 (17)	0.0814 (7)
H23A	−0.0434	0.8353	0.0812	0.098*
H23B	−0.0684	0.9724	0.1105	0.098*
C24	0.2312 (2)	0.78928 (19)	0.11634 (12)	0.0484 (4)
C25	0.2379 (3)	0.7110 (2)	0.05322 (15)	0.0645 (5)
H25	0.1613	0.6753	0.0513	0.077*
C26	0.3570 (3)	0.6860 (2)	−0.00634 (15)	0.0742 (7)
H26	0.3613	0.6325	−0.0476	0.089*
C27	0.4695 (3)	0.7399 (2)	−0.00493 (15)	0.0709 (6)
H27	0.5494	0.7241	−0.0458	0.085*
C28	0.4633 (2)	0.8177 (2)	0.05755 (13)	0.0553 (5)
H28	0.5396	0.8544	0.0577	0.066*
C29	0.34579 (18)	0.84291 (17)	0.12054 (11)	0.0424 (4)
N1	0.43033 (14)	0.90587 (15)	0.35091 (10)	0.0425 (3)
N2	0.10136 (15)	1.11034 (15)	0.43241 (10)	0.0443 (3)
H2A	0.0322	1.1202	0.4740	0.053*
O1	0.18613 (16)	1.19738 (15)	0.06779 (9)	0.0620 (4)
O2	0.13719 (13)	0.87891 (13)	0.44025 (9)	0.0485 (3)
O3	−0.09428 (12)	1.06941 (13)	0.25689 (11)	0.0578 (3)
O4	0.11530 (14)	0.80546 (15)	0.18039 (10)	0.0580 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0335 (7)	0.0489 (9)	0.0462 (9)	−0.0082 (6)	0.0004 (6)	−0.0184 (7)
C2	0.0332 (7)	0.0465 (8)	0.0389 (8)	−0.0142 (6)	0.0068 (6)	−0.0173 (6)
C3	0.0308 (6)	0.0425 (8)	0.0331 (7)	−0.0142 (6)	0.0034 (5)	−0.0146 (6)
C4	0.0322 (7)	0.0450 (8)	0.0327 (7)	−0.0149 (6)	0.0035 (5)	−0.0138 (6)
C5	0.0373 (7)	0.0472 (9)	0.0332 (7)	−0.0164 (6)	0.0040 (6)	−0.0145 (6)
C6	0.0411 (8)	0.0470 (9)	0.0372 (8)	−0.0161 (6)	−0.0008 (6)	−0.0155 (7)
C7	0.0540 (10)	0.0516 (10)	0.0590 (11)	−0.0134 (8)	0.0004 (8)	−0.0249 (9)
C8	0.0652 (12)	0.0455 (10)	0.0748 (13)	−0.0191 (9)	−0.0087 (10)	−0.0177 (9)
C9	0.0566 (10)	0.0537 (11)	0.0650 (12)	−0.0298 (9)	−0.0047 (9)	−0.0060 (9)
C10	0.0421 (8)	0.0575 (10)	0.0457 (9)	−0.0239 (7)	0.0010 (7)	−0.0118 (8)
C11	0.0362 (7)	0.0476 (9)	0.0349 (7)	−0.0173 (6)	−0.0013 (6)	−0.0131 (6)
C12	0.0524 (10)	0.0723 (13)	0.0457 (10)	−0.0122 (9)	−0.0117 (8)	−0.0177 (9)
C13	0.0430 (8)	0.0452 (9)	0.0363 (8)	−0.0167 (7)	−0.0014 (6)	−0.0146 (7)
C14	0.0421 (8)	0.0417 (8)	0.0416 (8)	−0.0087 (6)	−0.0092 (6)	−0.0149 (7)
C15	0.0617 (11)	0.0467 (10)	0.0551 (10)	−0.0153 (8)	−0.0118 (8)	−0.0146 (8)
C16	0.0753 (14)	0.0438 (10)	0.0839 (15)	−0.0058 (10)	−0.0191 (12)	−0.0251 (10)
C17	0.0628 (12)	0.0596 (13)	0.0836 (15)	0.0037 (10)	−0.0081 (11)	−0.0403 (11)
C18	0.0449 (9)	0.0651 (12)	0.0643 (12)	−0.0035 (8)	−0.0008 (8)	−0.0303 (10)
C19	0.0382 (8)	0.0463 (9)	0.0491 (9)	−0.0060 (7)	−0.0055 (7)	−0.0181 (7)
C20	0.0375 (8)	0.0751 (13)	0.0644 (12)	−0.0230 (8)	0.0119 (8)	−0.0223 (10)
C21	0.0538 (11)	0.0755 (14)	0.0874 (16)	−0.0374 (10)	0.0172 (10)	−0.0230 (12)
C22	0.0600 (13)	0.130 (2)	0.128 (2)	−0.0507 (15)	0.0145 (14)	−0.078 (2)
C23	0.0672 (13)	0.122 (2)	0.0594 (13)	−0.0371 (14)	−0.0041 (10)	−0.0318 (13)
C24	0.0565 (10)	0.0463 (9)	0.0401 (8)	−0.0138 (7)	−0.0013 (7)	−0.0165 (7)
C25	0.0839 (14)	0.0582 (11)	0.0545 (11)	−0.0209 (10)	−0.0098 (10)	−0.0262 (9)
C26	0.1009 (17)	0.0651 (13)	0.0479 (11)	−0.0059 (12)	−0.0087 (11)	−0.0327 (10)
C27	0.0766 (14)	0.0761 (14)	0.0452 (10)	−0.0013 (11)	0.0078 (9)	−0.0313 (10)
C28	0.0539 (10)	0.0605 (11)	0.0422 (9)	−0.0077 (8)	0.0070 (7)	−0.0206 (8)
C29	0.0443 (8)	0.0416 (8)	0.0350 (8)	−0.0073 (6)	0.0018 (6)	−0.0144 (6)
N1	0.0336 (6)	0.0514 (8)	0.0397 (7)	−0.0111 (5)	−0.0009 (5)	−0.0163 (6)
N2	0.0459 (7)	0.0519 (8)	0.0399 (7)	−0.0203 (6)	0.0139 (6)	−0.0205 (6)
O1	0.0688 (8)	0.0641 (8)	0.0401 (7)	−0.0195 (7)	0.0096 (6)	−0.0077 (6)
O2	0.0527 (7)	0.0497 (7)	0.0469 (6)	−0.0241 (5)	0.0162 (5)	−0.0168 (5)
O3	0.0342 (6)	0.0485 (7)	0.0844 (9)	−0.0120 (5)	0.0118 (6)	−0.0192 (6)
O4	0.0540 (7)	0.0760 (9)	0.0608 (8)	−0.0331 (6)	0.0075 (6)	−0.0345 (7)

Geometric parameters (Å, º) top

C1—N1	1.453 (2)	C15—C16	1.377 (3)
C1—C2	1.526 (2)	C15—H15	0.9300
C1—H1A	0.9700	C16—C17	1.380 (3)
C1—H1B	0.9700	C16—H16	0.9300
C2—C29	1.517 (2)	C17—C18	1.372 (3)
C2—C3	1.530 (2)	C17—H17	0.9300
C2—H2	0.9800	C18—C19	1.392 (2)
C3—C13	1.515 (2)	C18—H18	0.9300
C3—C4	1.5778 (19)	C19—O3	1.356 (2)
C3—H3	0.9800	C20—O3	1.426 (2)
C4—N1	1.4707 (18)	C20—C21	1.490 (3)
C4—C11	1.509 (2)	C20—H20A	0.9700
C4—C5	1.547 (2)	C20—H20B	0.9700
C5—O2	1.2227 (19)	C21—C22	1.488 (4)
C5—N2	1.350 (2)	C21—H21A	0.9700
C6—C7	1.376 (2)	C21—H21B	0.9700
C6—C11	1.388 (2)	C22—C23	1.466 (4)
C6—N2	1.405 (2)	C22—H22A	0.9700
C7—C8	1.390 (3)	C22—H22B	0.9700
C7—H7	0.9300	C23—O4	1.425 (2)
C8—C9	1.379 (3)	C23—H23A	0.9700
C8—H8	0.9300	C23—H23B	0.9700
C9—C10	1.388 (3)	C24—O4	1.387 (2)
C9—H9	0.9300	C24—C25	1.392 (2)
C10—C11	1.382 (2)	C24—C29	1.397 (2)
C10—H10	0.9300	C25—C26	1.375 (3)
C12—N1	1.457 (2)	C25—H25	0.9300
C12—H12A	0.9600	C26—C27	1.372 (3)
C12—H12B	0.9600	C26—H26	0.9300
C12—H12C	0.9600	C27—C28	1.381 (3)
C13—O1	1.211 (2)	C27—H27	0.9300
C13—C14	1.500 (2)	C28—C29	1.397 (2)
C14—C15	1.390 (2)	C28—H28	0.9300
C14—C19	1.398 (2)	N2—H2A	0.8600

N1—C1—C2	102.16 (13)	C15—C16—H16	120.4
N1—C1—H1A	111.3	C17—C16—H16	120.4
C2—C1—H1A	111.3	C18—C17—C16	121.00 (19)
N1—C1—H1B	111.3	C18—C17—H17	119.5
C2—C1—H1B	111.3	C16—C17—H17	119.5
H1A—C1—H1B	109.2	C17—C18—C19	119.7 (2)
C29—C2—C1	113.37 (13)	C17—C18—H18	120.2
C29—C2—C3	119.52 (12)	C19—C18—H18	120.2
C1—C2—C3	100.36 (12)	O3—C19—C18	123.51 (17)
C29—C2—H2	107.6	O3—C19—C14	116.14 (14)
C1—C2—H2	107.6	C18—C19—C14	120.32 (17)
C3—C2—H2	107.6	O3—C20—C21	106.46 (15)
C13—C3—C2	115.22 (12)	O3—C20—H20A	110.4
C13—C3—C4	114.19 (12)	C21—C20—H20A	110.4
C2—C3—C4	104.28 (11)	O3—C20—H20B	110.4
C13—C3—H3	107.6	C21—C20—H20B	110.4
C2—C3—H3	107.6	H20A—C20—H20B	108.6
C4—C3—H3	107.6	C22—C21—C20	116.2 (2)
N1—C4—C11	113.80 (12)	C22—C21—H21A	108.2
N1—C4—C5	114.13 (12)	C20—C21—H21A	108.2
C11—C4—C5	101.31 (12)	C22—C21—H21B	108.2
N1—C4—C3	103.47 (11)	C20—C21—H21B	108.2
C11—C4—C3	116.05 (12)	H21A—C21—H21B	107.4
C5—C4—C3	108.39 (11)	C23—C22—C21	119.24 (19)
O2—C5—N2	126.42 (14)	C23—C22—H22A	107.5
O2—C5—C4	125.33 (14)	C21—C22—H22A	107.5
N2—C5—C4	108.24 (13)	C23—C22—H22B	107.5
C7—C6—C11	122.42 (16)	C21—C22—H22B	107.5
C7—C6—N2	128.30 (16)	H22A—C22—H22B	107.0
C11—C6—N2	109.27 (14)	O4—C23—C22	112.6 (2)
C6—C7—C8	117.32 (18)	O4—C23—H23A	109.1
C6—C7—H7	121.3	C22—C23—H23A	109.1
C8—C7—H7	121.3	O4—C23—H23B	109.1
C9—C8—C7	121.11 (18)	C22—C23—H23B	109.1
C9—C8—H8	119.4	H23A—C23—H23B	107.8
C7—C8—H8	119.4	O4—C24—C25	119.57 (17)
C8—C9—C10	120.86 (18)	O4—C24—C29	119.84 (14)
C8—C9—H9	119.6	C25—C24—C29	120.44 (18)
C10—C9—H9	119.6	C26—C25—C24	120.5 (2)
C11—C10—C9	118.67 (17)	C26—C25—H25	119.7
C11—C10—H10	120.7	C24—C25—H25	119.7
C9—C10—H10	120.7	C27—C26—C25	120.12 (19)
C10—C11—C6	119.61 (16)	C27—C26—H26	119.9
C10—C11—C4	131.19 (15)	C25—C26—H26	119.9
C6—C11—C4	109.15 (13)	C26—C27—C28	119.6 (2)
N1—C12—H12A	109.5	C26—C27—H27	120.2
N1—C12—H12B	109.5	C28—C27—H27	120.2
H12A—C12—H12B	109.5	C27—C28—C29	122.0 (2)
N1—C12—H12C	109.5	C27—C28—H28	119.0
H12A—C12—H12C	109.5	C29—C28—H28	119.0
H12B—C12—H12C	109.5	C28—C29—C24	117.34 (16)
O1—C13—C14	119.75 (15)	C28—C29—C2	116.07 (15)
O1—C13—C3	120.24 (14)	C24—C29—C2	126.43 (14)
C14—C13—C3	119.99 (13)	C1—N1—C12	115.49 (14)
C15—C14—C19	118.30 (16)	C1—N1—C4	108.59 (11)
C15—C14—C13	117.35 (16)	C12—N1—C4	116.17 (13)
C19—C14—C13	124.35 (14)	C5—N2—C6	111.76 (13)
C16—C15—C14	121.4 (2)	C5—N2—H2A	124.1
C16—C15—H15	119.3	C6—N2—H2A	124.1
C14—C15—H15	119.3	C19—O3—C20	121.51 (14)
C15—C16—C17	119.2 (2)	C24—O4—C23	117.83 (15)

N1—C1—C2—C29	−174.22 (12)	C14—C15—C16—C17	1.6 (3)
N1—C1—C2—C3	−45.56 (14)	C15—C16—C17—C18	−2.3 (3)
C29—C2—C3—C13	−74.68 (18)	C16—C17—C18—C19	0.4 (3)
C1—C2—C3—C13	160.78 (13)	C17—C18—C19—O3	−175.51 (17)
C29—C2—C3—C4	159.35 (13)	C17—C18—C19—C14	2.3 (3)
C1—C2—C3—C4	34.82 (14)	C15—C14—C19—O3	175.02 (14)
C13—C3—C4—N1	−138.67 (13)	C13—C14—C19—O3	−4.5 (2)
C2—C3—C4—N1	−12.05 (15)	C15—C14—C19—C18	−2.9 (2)
C13—C3—C4—C11	−13.29 (17)	C13—C14—C19—C18	177.56 (15)
C2—C3—C4—C11	113.32 (14)	O3—C20—C21—C22	−73.7 (2)
C13—C3—C4—C5	99.82 (14)	C20—C21—C22—C23	68.2 (3)
C2—C3—C4—C5	−133.56 (13)	C21—C22—C23—O4	54.5 (4)
N1—C4—C5—O2	−51.95 (19)	O4—C24—C25—C26	−175.97 (17)
C11—C4—C5—O2	−174.67 (14)	C29—C24—C25—C26	−0.4 (3)
C3—C4—C5—O2	62.75 (18)	C24—C25—C26—C27	−0.8 (3)
N1—C4—C5—N2	127.34 (14)	C25—C26—C27—C28	0.8 (3)
C11—C4—C5—N2	4.62 (15)	C26—C27—C28—C29	0.4 (3)
C3—C4—C5—N2	−117.96 (13)	C27—C28—C29—C24	−1.6 (3)
C11—C6—C7—C8	−0.6 (3)	C27—C28—C29—C2	174.00 (16)
N2—C6—C7—C8	179.12 (15)	O4—C24—C29—C28	177.14 (15)
C6—C7—C8—C9	−0.2 (3)	C25—C24—C29—C28	1.6 (2)
C7—C8—C9—C10	0.5 (3)	O4—C24—C29—C2	2.0 (3)
C8—C9—C10—C11	0.1 (3)	C25—C24—C29—C2	−173.54 (16)
C9—C10—C11—C6	−0.8 (2)	C1—C2—C29—C28	−91.08 (17)
C9—C10—C11—C4	176.26 (15)	C3—C2—C29—C28	150.90 (15)
C7—C6—C11—C10	1.1 (2)	C1—C2—C29—C24	84.06 (19)
N2—C6—C11—C10	−178.63 (13)	C3—C2—C29—C24	−34.0 (2)
C7—C6—C11—C4	−176.56 (14)	C2—C1—N1—C12	172.65 (14)
N2—C6—C11—C4	3.68 (16)	C2—C1—N1—C4	40.12 (15)
N1—C4—C11—C10	54.8 (2)	C11—C4—N1—C1	−144.11 (13)
C5—C4—C11—C10	177.73 (15)	C5—C4—N1—C1	100.27 (15)
C3—C4—C11—C10	−65.1 (2)	C3—C4—N1—C1	−17.30 (16)
N1—C4—C11—C6	−127.89 (13)	C11—C4—N1—C12	83.73 (18)
C5—C4—C11—C6	−4.94 (14)	C5—C4—N1—C12	−31.89 (19)
C3—C4—C11—C6	112.18 (14)	C3—C4—N1—C12	−149.46 (14)
C2—C3—C13—O1	−4.4 (2)	O2—C5—N2—C6	176.50 (14)
C4—C3—C13—O1	116.34 (16)	C4—C5—N2—C6	−2.78 (17)
C2—C3—C13—C14	177.33 (13)	C7—C6—N2—C5	179.74 (16)
C4—C3—C13—C14	−61.97 (17)	C11—C6—N2—C5	−0.52 (17)
O1—C13—C14—C15	−34.4 (2)	C18—C19—O3—C20	10.7 (3)
C3—C13—C14—C15	143.95 (15)	C14—C19—O3—C20	−167.11 (16)
O1—C13—C14—C19	145.16 (17)	C21—C20—O3—C19	171.34 (17)
C3—C13—C14—C19	−36.5 (2)	C25—C24—O4—C23	−56.2 (3)
C19—C14—C15—C16	1.0 (3)	C29—C24—O4—C23	128.2 (2)
C13—C14—C15—C16	−179.46 (16)	C22—C23—O4—C24	157.44 (19)

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C14–C19 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	1.96	2.8105 (17)	170
C26—H26···Cg4ⁱⁱ	0.93	2.91	3.617 (3)	134

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₂₉H₂₈N₂O₄
M_r	468.53
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.4223 (3), 10.5115 (3), 14.1754 (5)
α, β, γ (°)	70.235 (2), 87.309 (3), 69.065 (2)
V (Å³)	1229.67 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.22 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008)
T_min, T_max	0.979, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	22180, 5998, 4260
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.147, 1.01
No. of reflections	5998
No. of parameters	317
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.27

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C14–C19 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	1.96	2.8105 (17)	169.9
C26—H26···Cg4ⁱⁱ	0.93	2.91	3.617 (3)	134

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y+2, −z.

Acknowledgements

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection. SN thanks the University Grant Commission (UGC), Government of India, New Delhi, for a Meritorious Fellowship under the SAP programme.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ganesh, G., Yuvaraj, P. S., Govindan, E., Reddy, B. S. R. & SubbiahPandi, A. (2012). Acta Cryst. E68, o2902–o2903. CSD CrossRef CAS IUCr Journals Google Scholar
Narayanan, S., Srinivasan, T., Purushothaman, S., Raghunathan, R. & Velmurugan, D. (2012). Acta Cryst. E68, o3345. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Waldmann, H. (1995). Synlett, pp. 133–141. CrossRef Google Scholar

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Volume 68| Part 12| December 2012| Page o3344

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4′-Methyl-1H-14′,19′-dioxa-4′-aza­spiro­[indole-3,5′-tetra­cyclo­[18.4.0.02,6.08,13]tetra­cosa­ne]-1′(24′),8′,10′,12′,20′,22′-hexa­ene-2,7′(3H)-dione

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4′-Methyl-1H-14′,19′-dioxa-4′-azaspiro[indole-3,5′-tetracyclo[18.4.0.0^2,6.0^8,13]tetracosane]-1′(24′),8′,10′,12′,20′,22′-hexaene-2,7′(3H)-dione